US6451910B1 - Acrylic premix, acrylic artificial marble and production method thereof - Google Patents

Acrylic premix, acrylic artificial marble and production method thereof Download PDF

Info

Publication number
US6451910B1
US6451910B1 US09/698,046 US69804600A US6451910B1 US 6451910 B1 US6451910 B1 US 6451910B1 US 69804600 A US69804600 A US 69804600A US 6451910 B1 US6451910 B1 US 6451910B1
Authority
US
United States
Prior art keywords
acrylic
parts
weight
formula
functional monomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US09/698,046
Other languages
English (en)
Inventor
Seiya Koyanagi
Shinji Saiki
Yuichiro Kishimoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Rayon Co Ltd
Original Assignee
Mitsubishi Rayon Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Rayon Co Ltd filed Critical Mitsubishi Rayon Co Ltd
Assigned to MITSUBISHI RAYON CO., LTD. reassignment MITSUBISHI RAYON CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KISHIMOTO, YUICHIRO, KOYANAGI, SEIYA, SAIKI, SHINJI
Application granted granted Critical
Publication of US6451910B1 publication Critical patent/US6451910B1/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/06—Acrylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/54—Substitutes for natural stone, artistic materials or the like
    • C04B2111/542—Artificial natural stone
    • C04B2111/545—Artificial marble

Definitions

  • the present invention relates to an acrylic premix which can provide an acrylic SMC (sheet molding compound) or BMC (bulk molding compound) which is suited for molding at high temperature and has excellent molding processability, thickening property and storage stability; acrylic artificial marble excellent in appearance and impact resistance; and a method for producing acrylic artificial marble which gives high productivity.
  • an acrylic SMC sheet molding compound
  • BMC bulk molding compound
  • Acrylic artificial marble prepared by compounding inorganic fillers such as aluminum hydroxide and the like into an acrylic resin has various prominent functions and properties such as excellent appearance, soft feeling, weatherability and the like of a molded article and is widely used for counters such as a kitchen counter and the like, washing and dressing stands, waterproof pan, and other architectural uses. These are usually produced by a casting method in which a so-called premix prepared by dispersing inorganic fillers into an acrylic syrup composed of acrylic monomers containing methyl methacrylate and of an acrylic polymer is filled into a mold, and this is cured and polymerized at relatively lower temperature.
  • JP-B Japanese Patent Application Publication
  • JP-B No. 4-58423 disclosed artificial marble molded article excellent in heat-resistance and flexibility obtained by a casting method wherein a premix comprising aluminum hydroxide and syrup components composed of a methacrylate, aromatic vinyl compound and specific polyalkylenepolyol di(meth)acrylate is cured for long period of time (3 hours) at a temperature of 80° C.
  • Japanese Patent Application Laid-Open (JP-A) No. 6-298883 discloses an acrylic BMC for artificial marble excellent in low shrinkage property in heat-curing, prepared by compounding a thermoplastic acrylic resin powder which is poorly soluble in an acrylic syrup.
  • Japanese Patent Application Laid-Open (JP-A) No. 6-313019 discloses an acrylic BMC for artificial marble produced by compounding into an acrylic syrup a resin powder prepared by spray-drying a cross-linked polymer obtained by emulsion polymerization, cracking in molding the BMC being prevented and appearance and thickening stability of a molded article made of the BMC being improved.
  • An object of the present invention is to provide an acrylic premix which can provide an acrylic SMC (sheet molding compound) or BMC (bulk molding compound) which is suited for molding at high temperature and has excellent molding processability, thickening property and storage stability; acrylic artificial marble excellent in appearance and impact resistance; and a method for producing acrylic artificial marble which gives high productivity.
  • the present inventors have intensively investigated for attaining the above-described object, and as a result, have found that excellent effects can be obtained by compounding an acrylic poly-functional monomer having specific structure, completing the present invention.
  • the present invention relates to an acrylic premix comprising 10 to 90% by weight of an acrylic resin composition (A) comprising an acrylic mono-functional monomer (a1), an acrylic poly-functional monomer (a2) containing at least one compound represented by any of the following general formulae (I) to (IV), and an acrylic polymer (b); 10 to 90% by weight of an inorganic filler (B); and 0.01 to 10 parts by weight of a curing agent (C) based on 100 parts by weight of the total amount of the acrylic resin composition (A) and the inorganic filler (B); acrylic artificial marble obtained by curing this acrylic premix; and a method for producing acrylic artificial marble comprising curing this acrylic premix with pressing and heating at a temperature from 90° C. to 150° C.
  • R 1 represents a hydrogen atom or a methyl group, and k represents an integer from 3 to 30.
  • R 1 represents a hydrogen atom or a methyl group, and each of 1 and m represents an integer from 0 to 25 and 1+m is 2 to 25.
  • R 1 represents a hydrogen atom or a methyl group, and n represents an integer from 2 to 25.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 to R 5 represent an alkylene group having 1 to 10 carbon atoms
  • each of p, q and r represents an integer from 0 to 10 and p+q+r is 2 to 25).
  • FIG. 1 is a schematic view showing a frame made of SUS used in measuring falling ball impact height.
  • the acrylic resin composition (A) used in the present invention comprises an acrylic mono-functional monomer (a1), an acrylic poly-functional monomer (a2) and an acrylic polymer (b).
  • the amount used of the acrylic resin composition (A) is in the range from 10 to 90% by weight based on the total amount of the acrylic premix of the present invention.
  • the reason for this is that when the content of the component (A) is 10% by weight or more, there are tendencies that flowability in molding an acrylic premix is excellent, loose holes and whitening are not formed even if a molded article in complicated form is made, and gloss and impact-resistance of the resulting molded article are excellent. Another reason for this is that when the content of the component (A) is 90% by weight or less, there are tendencies that shrinkage rate in curing decreases, and appearance of a molded article having deep texture specific to marble (clear feeling) is obtained in this range.
  • the lower limit of this content is preferably 20% by weight or more, particularly preferably 30% by weight or more.
  • the upper limit of this content is preferably 80% by weight or less, particularly preferably 60% by weight or less.
  • the acrylic mono-functional monomer (a1) constituting the acrylic resin composition (A) is not particularly restricted providing it is a mono-functional monomer having a methacryloyl and/or acryloyl group or a mixture thereof.
  • examples thereof include methyl (meth)acrylate, alkyl (meth)acrylates having 2 to 20 carbon atoms, hydroxyalkyl (meth)acrylates having a hydroxyalkyl group having 1 to 20 carbon atoms, (meth)acrylates having an ester group carrying an aromatic ring such as benzyl (meth)acrylate and the like, (meth)acrylates having an ester group carrying a cyclohexane ring such as cyclohexyl (meth)acrylate and the like, (meth)acrylates having an ester group carrying a bicyclo ring such as isobornyl (meth)acrylate and the like, (meth)acrylates having an ester group carrying a tricyclo ring such as tricyclo[5.2
  • the acrylic resin composition (A) may contain mono-functional monomers other than acrylic mono-functional monomers, such as aromatic vinyl compounds like styrene and the like, vinyl acetate, (meth)acrylonitrile, vinyl chloride, maleic anhydride, maleic acid, maleates, fumaric acid, fumarates and the like, in addition to the acrylic mono-functional monomer (a1). These various mono-functional monomers may be optionally used alone or in combination of two or more.
  • methyl methacrylate in particular as the acrylic mono-functional monomer (a1) is preferable since then the resulting molded article may tend to be endowed with deep texture specific to marble (clear feeling).
  • use of methyl methacrylate together with at least one (meth)acrylate selected from (meth)acrylates having an ester group carrying a hydroxyalkyl group having 2 to 6 carbon atoms, (meth)acrylates having an ester group carrying a benzene ring, (meth)acrylates having an ester group carrying a cyclohexane ring, (meth)acrylates having an ester group carrying a bicyclo ring, (meth)acrylates having an ester group carrying a tricyclo ring, (meth)acrylates having an ester group carrying a fluorine atom and (meth)acrylates having an ester group having cyclic ether structure is further preferable since then gloss unevenness on a molded article tends to decrease.
  • the content of the component (a1) is not particularly restricted, and preferably in the range from 1 to 50% by weight based on the total amount of the acrylic premix of the present invention.
  • the lower limit of the content of the component (a1) is more preferably 5% by weight or more, and the upper limit thereof is preferably 30% by weight or less.
  • the content of methyl methacrylate is preferably in the range from 1 to 20% by weight based on the total amount of the acrylic premix of the present invention, and the lower limit of the content of methyl methacrylate is more preferably 5% by weight or more, and the upper limit thereof is preferably 15% by weight or less.
  • the acrylic poly-functional monomer (a2) constituting the acrylic resin composition (A) is an acrylic poly-functional monomer containing at least one compound represented by any of the above-described general formulae (I) to (IV).
  • the acrylic poly-functional monomer (a2) contains at least one compound represented by any of the above-described general formulae (I) to (IV), a molded article can be endowed with excellent impact-resistance, high gloss, high deflection temperature under load and hot water-resistance.
  • the acrylic poly-functional monomer (a2) contains at least one compound represented by any of the above-described general formulae (I) to (IV)
  • a molded article can be endowed with excellent impact-resistance, high gloss, high deflection temperature under load and hot water-resistance.
  • use of at least one compound represented by any of the above-described general formulae (II) to (IV) is preferable since then particularly hot water-resistance of a molded article is excellent.
  • k is required to be 3 to 30. The reason for this is that when k is in this range, impact-resistance of a molded article is excellent.
  • the lower limit of k is preferably 10 or more, more preferably 12 or more.
  • the upper limit of k is preferably 28 or less, more preferably 25 or less.
  • k of 4 or less is preferable since then deflection temperature under load and gloss of a molded article tend to be higher, molding property at a high temperature of 90° C. or more tends to be excellent and hot water-resistance of a molded article also tends to be excellent, and particularly k of 3 is more preferable since then deflection temperature under load of a molded article is higher.
  • the l+m is in the range from 2 to 25.
  • the reason for this is that when l+m is 2 or more, impact-resistance of a molded article is excellent, and when l+m is 25 or less, deflection temperature under load and gloss of a molded article are higher enabling molding at a high temperature of 90° C. or more. Further, when l+m is 25 or less, hot water-resistance of a molded article is excellent.
  • the lower limit of l+m is preferably 3 or more, more preferably 5 or more.
  • the upper limit of l+m is preferably 15 or less, more preferably 10 or less.
  • n is in the range from 2 to 25.
  • the reason for this is that when n is 2 or more, impact-resistance of a molded article is excellent, and when n is 25 or less, deflection temperature under load and gloss of a molded article are higher enabling molding at a high temperature of 90° C. or more. Further, when n is 25 or less, hot water-resistance of a molded article is excellent.
  • the lower limit of n is preferably 3 or more, more preferably 4 or more.
  • the upper limit of n is preferably 15 or less, more preferably 10 or less.
  • p+q+r is in the range from 2 to 25.
  • the reason for this is that when p+q+r is 2 or more, impact-resistance of a molded article is excellent, and when p+q+r is 25 or less, deflection temperature under load and gloss of a molded article are higher enabling molding at a high temperature of 90° C. or more.
  • the lower limit of p+q+r is preferably 3 or more.
  • the upper limit of p+q+r is preferably 15 or less, more preferably 10 or less, most preferably 7 or less.
  • R 2 to R 5 represent an alkylene group having 1 to 10 carbon atoms. Particularly, a pentylene group, dimethylethylene group and dimethylpropylene group are preferable.
  • acrylic poly-functional monomer (a2) compounds represented by any of the general formulae (I) to (IV) may be used alone or in combination of two or more. Further, other acrylic poly-functional monomer may be used together with one compound represented by any of the general formulae (I) to (IV).
  • Examples of the other acrylic poly-functional monomer include a compound represented by the general formula (I) wherein k is 1, ethylene glycol di(meth)acrylate; a compound represented by the general formula (I) wherein k is 2, diethylene glycol di(meth)acrylate; a compound represented by the general formula (I) wherein k is 31 or more, polyethylene glycol di(meth)acrylate; a compound represented by the general formula (II) wherein l+m is 1, propylene glycol di(meth)acrylate; a compound represented by the general formula (II) wherein l+m is 26 or more, polypropylene glycol di(meth)acrylate; a compound represented by the general formula (III) wherein n is 1,1,4-butylene glycol di(meth)acrylate; compounds represented by the general formula (III) wherein n is 26 or more, polybutylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, n
  • acrylic resin composition (A) may also contain poly-functional monomers other then acrylic poly-functional monomers, such as divinylbenzene, triaryl isocyanurate and the like, in addition to the acrylic poly-functional monomer (a2).
  • poly-functional monomers such as divinylbenzene, triaryl isocyanurate and the like, in addition to the acrylic poly-functional monomer (a2).
  • These various poly-functional monomers may be optionally used alone or in combination of two or more.
  • this compound together with at least one compound selected from the group consisting of ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate and trimethylolpropane tri(meth)acrylate.
  • a molded article can be endowed with high impact-resistance, simultaneously with high deflection temperature under load and high gloss, molding at a high temperature of 90° C. or more is made possible, further, excellent hot water-resistance can be imparted to a molded article.
  • the content of at least one compound represented by any of the general formulae (I) to (IV) is not particularly restricted, and preferably in the range from 0.1 to 30% by weight based on the total amount of the acrylic premix of the present invention.
  • this content is 0.1% by weight or more, impact-resistance of a molded article tends to be excellent, and when it is 30% by weight or less, deflection temperature under load of a molded article tends to be higher.
  • the lower limit of this content is preferably 0.5% by weight or more, particularly preferably 1% by weight or more.
  • the upper limit of this content is preferably 20% by weight or less, particularly preferably 10% by weight or less.
  • the amount used of the acrylic poly-functional monomer (a2) is not particularly restricted, and preferably in the range from 0.1 to 30% by weight based on the total amount of the acrylic premix of the present invention.
  • the content of the component (a2) is 0.1% by weight or more, impact-resistance and gloss of a molded article tend to be excellent, and when it is 30% by weight or less, processability of a molded article tends to excellent.
  • the lower limit of this content is more preferably 1% by weight or more, and the upper limit of this content is more preferably 20% by weight or less.
  • the acrylic polymer (b) constituting the acrylic resin composition (A) is a component which imparts to the acrylic premix of the present invention suitable viscosity, also is a thickening component which imparts to the acrylic premix of the present invention excellent viscosity providing excellent handling property without stickiness when the acrylic premix is used as a SMC or BMC, further is a component which imparts to a molded article made of the acrylic artificial marble of the present invention high strength.
  • constituent components (monomers used for polymerization, and the like) of the acrylic polymer (b) there can be used for example the same compounds as the above-described acrylic mono-functional monomer (a1) and the other mono-functional monomer.
  • the acrylic polymer (b) there may be used a homopolymer obtained by homo-polymerization of a monomer or a copolymer obtained by using two or more monomers together. If necessary, there may be used cross-linked polymers obtained by copolymerization of the above-described acrylic poly-functional monomer (a2) and other poly-functional monomer.
  • the content of the acrylic polymer (b) is not particularly restricted, and preferably in the range from 0.1 to 30% by weight based on the total amount of the acrylic premix of the present invention in view of handling property of the acrylic premix of the present invention, degree of thickening when this premix is used as an acrylic SMC or BMC, mechanical strength of the acrylic artificial marble of the present invention, and the like.
  • the content of the component (b) is 0.1% by weight or more, high thickening effect tends to be manifested, and handling property of the acrylic premix or acrylic SMC or BMC tends to be excellent.
  • the content of the component (b) is 30% by weight or less, kneading property of the acrylic premix or acrylic SMC or BMC tends to be excellent.
  • the lower limit of this content is preferably 1% by weight or more, particularly preferably 5% by weight or more.
  • the upper limit of this content is preferably 25% by weight or less, particularly preferably 20% by weight or less.
  • the acrylic polymer (b) may be a cross-linked polymer or non-cross-linked polymer and can be appropriately selected optionally, and it is preferable that the weight-average molecular weight thereof is in the range from 15,000 to 5,000,000 in view of flowability of the acrylic premix or the acrylic SMC or BMC of the present invention, and mechanical strength of the acrylic artificial marble of the present invention.
  • the weight-average molecular weight herein referred to means a value in terms of polystyrene according to GPC and it is a value obtained by appropriately changing measuring conditions as described in the following examples depending on the range of the weight-average molecular weight.
  • the acrylic polymer (b) can be produced by a solution polymerization method, bulk polymerization method, emulsion polymerization method, suspension polymerization method and the like.
  • the acrylic premix of the present invention is used as an acrylic SMC or BMC, a thickening agent is necessary.
  • the thickening agent used is not particularly restricted, and there can be for example used a magnesium oxide powder, polymer powder and the like. Wherein, use of a polymer powder is preferable since then hot water-resistance of a molded article tends to be excellent.
  • a part or all of the acrylic polymer (b) may be used as the thickening agent.
  • the polymer powder which can be used as a thickening agent is not particularly restricted and optionally can be selected appropriately.
  • use of a polymer powder having a bulk density of 0.1 to 0.7 g/ml and an oil absorption of linseed oil of 60 to 200 ml/100 g as the acrylic polymer (b) is preferable since then thickening in a short period of time is realized and an acrylic SMC or BMC excellent in handling property and productivity is obtained.
  • the lower limit of this bulk density is more preferably 0.15 g/ml, particularly preferably 0.2 g/ml or more.
  • the upper limit thereof is more preferably 0.65 g/ml or less, particularly preferably 0.6 g/ml or less.
  • the polymer powder has an oil absorption of linseed oil of 60 ml/100 g or more, there are tendencies that sufficient thickening effect can be obtained with a small amount of the polymer powder used and thickening is carried out in a short period of time, therefore, productivity increases leading to advantage in cost.
  • this oil absorption is 200 ml/100 g or less, kneading property in producing an acrylic SMC or BMC tends to be excellent since then dispersibility of the polymer powder becomes excellent.
  • the lower limit of this oil absorption is more preferably 70 ml/100 g or more, particularly preferably 80 ml/100 g or more.
  • the lower limit thereof is more preferably 180 ml/100 g or less, particularly preferably 160 ml/100 g or less.
  • the degree of swelling by methyl methacrylate of the polymer powder is not particularly restricted, and preferably 1-fold or less or 20-fold or more.
  • this degree of swelling is 1-fold or less or 20-fold or more, there are tendencies that speed of dissolving into the acrylic mono-functional monomer (a1) and/or acrylic poly-functional monomer (a2) increases, thickening speed increases, accordingly thickening in a short period of time is possible and productivity of an acrylic BMC increases.
  • the degree of swelling herein referred to is given as follows.
  • a polymer powder is charged into a 100 ml measuring cylinder, compacted by soft tapping several times by 5 ml, then, methyl methacrylate which has been cooled to 10° C. or less is charged therein so that the total amount reaches 100 ml, the mixture is stirred quickly so as to obtain whole uniformity, then, the measuring cylinder is kept in a constant temperature vessel at 25° C. for 1 hour, the volume of the polymer layer (polymer containing methyl methacrylate) at that time is measured and the ratio of this value to volume (5 ml) of the original polymer powder layer.
  • the whole volume of 100 ml after kept under this condition can be regarded as a polymer layer containing methyl methacrylate, and this polymer layer containing methyl methacrylate depends on the volume of a measuring cylinder used, therefore in this case, the degree of swelling s defined as 20-fold or more.
  • the degree of swelling is a value of 1 or less.
  • This polymer powder may be a non-cross-linked polymer powder or a cross-linked polymer powder, and preferably a non-cross-linked polymer powder.
  • the non-cross-linked polymer powder herein referred to means a polymer powder at least of which surface part is constituted of a non-cross-linked polymer powder.
  • the polymer powder may have so-called core-shell structure composed of core phase and shell phase having mutually different chemical compositions, structures, molecular weights and the like of polymers constituting the phases.
  • the core phase may be made of a non-cross-linked polymer or a cross-linked polymer, however, the shell phase is preferably made of a non-cross-linked polymer.
  • the weight-average molecular weight of the polymer powder used as a thickening agent is not particularly restricted. Wherein, it is preferable that the weight-average molecular weight of the polymer powder is 100,000 or more in view of balance between thickening effect and thickening time.
  • the lower limit of this weight-average molecular weight of the polymer powder is preferably 300,000 or more, particularly preferably 500,000 or more.
  • the upper limit thereof is preferably 5,000,000 or less, more preferably 4,500,000 or less, particularly preferably 4,000,000 or less.
  • the specific surface area of the polymer powder used as a thickening agent is not particularly restricted, and preferably in the range from 0.5 to 100 m 2 /g.
  • the reason for this is that when the specific surface area of the polymer powder is 0.5 m 2 /g or more, there is tendency that sufficient thickening effect is obtained by use of a small amount of the polymer powder and thickening tends to be accomplished in a short period of time, leading to improved productivity.
  • the reason for this is hypothesized that since this polymer powder has a large specific surface area as described above, the polymer is dissolved quickly into an acrylic mono-functional monomer (a1) and/or an acrylic poly-functional monomer (a2), obtaining thickening effect in a short period of time.
  • this specific surface area is 100 m 2 /g or less, dispersibility of the polymer powder in an acrylic mono-functional monomer (a1) and/or an acrylic poly-functional monomer (a2) is excellent, therefore, there is a tendencies that handling in thickening is excellent and kneading property in producing an acrylic premix is excellent.
  • the lower limit of this specific surface area is more preferably 1 m 2 /g or more, and the upper limit thereof is more preferably 80 m 2 /g or less.
  • the average particle size of the polymer powder used as a thickening agent is not particularly restricted, and preferably in the range from 1 to 500 ⁇ m.
  • the lower limit of this average particle size is more preferably 5 ⁇ m or more, particularly preferably 10 ⁇ m or more.
  • the upper limit thereof is more preferably 350 ⁇ m or less, particularly preferably 200 ⁇ m or less.
  • the polymer powder used as a thickening agent is preferably a secondary agglomerate formed by agglomeration of primary particles.
  • the polymer powder is a secondary agglomerate, there are tendencies that absorption speed of an acrylic mono-functional monomer (a1) and/or an acrylic poly-functional monomer (a2) is high and thickening property is extremely excellent.
  • the average particle size of the primary particle of the polymer powder is preferably in the range from 0.03 to 1 ⁇ m.
  • this average particle size is in the range from 0.03 to 1 ⁇ m, there are tendencies that sufficient thickening effect is obtained with a small amount of the polymer powder used and thickening can be accomplished in a short period of time, leading to increase in productivity.
  • the lower limit of the average particle size of the primary particle is more preferably 0.07 ⁇ m or more, and the upper limit thereof is more preferably 0.7 ⁇ m or less.
  • Production method of the polymer powder used as a thickening agent is not particularly restricted, and the polymer powder can be produced by a known polymerization method. Among them, a method in which an emulsion obtained by emulsion polymerization is subjected to spray drying, freeze drying, acid/salt coagulation and the like to obtain a polymer powder is preferable since a polymer powder having the above-described specific bulk density and oil absorption can be produced efficiently.
  • the inorganic filler (B) used in the present invention is a component which imparts marble-like deep texture (clearness) and heat-resistance to an acrylic artificial marble molded article obtained by molding the acrylic premix of the present invention.
  • the amount used of the inorganic filler (B) is in the range from 10 to 90% by weight based on the total amount of the acrylic premix of the present invention. When this amount used is 10% by weight or more, the resulting molded article has excellent texture, heat-resistance and the like, and shrinkage rate in curing decreases. On the other hand, when this amount used is 90% by weight or less, flowability in molding an acrylic premix and an acrylic SMC or BMC tends to be excellent, and the resulting acrylic artificial marble molded article has excellent gloss and impact-resistance.
  • the lower limit of this amount used is more preferably 20% by weight or more, particularly preferably 30% by weight or more.
  • the upper limit thereof is more preferably 80% by weight or less, particularly preferably 70% by weight or less.
  • the inorganic filler (B) is not particularly restricted, and there can be used, for example, aluminum hydroxide, silica, amorphous silica, calcium carbonate, barium sulfate, titanium oxide, calcium phosphate, talc, clay, mica, glass powder and the like. These may be optionally selected appropriately for use, and two or more may be used together. Among them, aluminum hydroxide, calcium carbonate, silica, amorphous silica, and glass powder are preferable in view of texture of the resulting molded article.
  • the curing agent (C) used in the present invention is not particularly restricted, and there can be used, for example, radical polymerization initiators such as organic peroxides, azo compounds, and the like.
  • the curing agent (C) is used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the total amount of the acrylic resin composition (A) and the inorganic filler (B).
  • this amount used is 0.01 part by weight or more, curing property of the acrylic premix of the present invention is sufficient, and when it is 10 parts by weight or less, storage stability of the acrylic premix is excellent.
  • curing agents having a 10 hours half life time of 75° C. or more are preferable among other.
  • a curing agent having a 10 hours half life time of 75° C. or more is used, there is a tendency that curing of an acrylic premix in a short period of time is made possible and storage stability of an acrylic premix is excellent.
  • the acrylic premix of the present invention comprises the above-described components (A) to (C) as basic constituent components, and a granite-like artificial marble molded article having grain pattern can be obtained by compounding an inorganic filler-containing resin particle (D) into the basic components and molding the mixture.
  • the amount used of the inorganic filler-containing resin particle (D) is not particularly restricted, and preferably in the range from 1 to 50% by weight based on the total amount of the acrylic premix.
  • this amount used is 1% by weight or more, grain pattern having excellent design tends to be obtained, and when it is 50% by weight or less, kneading property in producing the acrylic premix tends to be excellent.
  • the lower limit of this amount used is more preferably 3% by weight or more, particularly preferably 5% by weight or more.
  • the upper limit thereof is more preferably 40% by weight or less, particularly preferably 30% by weight or less.
  • the resin constituting the inorganic filler-containing resin particle (D) is not particularly restricted providing it is a resin which is not dissolved in methyl methacrylate, and examples thereof include cross-linked acrylic resins, cross-linked polyester resins, cross-linked styrene resins and the like.
  • a cross-linked acrylic resin is preferable since it has high affinity with the acrylic resin composition (A) and a molded article having beautiful appearance is obtained using this resin.
  • This cross-linked acrylic resin may be a resin containing a non-cross-linked acrylic polymer.
  • the content of the resin in the inorganic filler-containing resin particle (D) is not particularly restricted, and preferably in the range from 10 to 90% by weight based on the total amount of the component (D).
  • this content is 10 parts by weight or more, there is tendency that a molded article having higher strength can be obtained, and when it is 90 arts by weight or less, texture, heat-resistance and the like of the resulting molded article tend to be excellent.
  • the total amount of the resin component in the inorganic filler-containing resin particle (D) and the acrylic resin composition (A) is preferably in the range from 10 to 90% by weight based on the total amount of the acrylic premix of the present invention.
  • this total amount is 10% by weight or more, there are tendencies that flowability in molding the acrylic premix is improved, loose holes and whitening are not easily formed even if a molded article in complicated form is made, and gloss and impact-resistance of the resulting molded article are excellent.
  • this total amount is 90% by weight or less, shrinkage rate in curing tends to lower.
  • this total amount is in the range from 10 to 90% by weight, there is tendency that appearance of a molded article having marble-like deep texture (clearness) can be obtained.
  • the lower limit of this total amount is preferably 20% by weight or more, particularly preferably 30% by weight or more.
  • the upper limit thereof is more preferably 80% by weight or less, particularly preferably 60% by weight or less.
  • the inorganic filler constituting the inorganic filler-containing resin particle (D) is not particularly restricted, and there can be used for example a variety of the inorganic fillers listed above as examples of the inorganic filler (B). They can be used in combination of two or more. Further, there can be used different inorganic fillers from the inorganic filler-containing resin particle (D) and the inorganic filler (B).
  • the content of the inorganic filler in the inorganic filler-containing resin particle (D) is not particularly restricted, and preferably in the range from 10 to 90% by weight based on the total amount of the component (D).
  • this content is 10% by weight or more, texture, heat-resistance and the like of the resulting molded article tend to be excellent, and when it is 90 arts by weight or less, there is tendency that a molded article having higher strength can be obtained.
  • the total amount of the inorganic filler in the inorganic filler-containing resin particle (D) and the inorganic filler (B) described above is preferably in the range from 10 to 90% by weight based on the total amount of the acrylic premix of the present invention.
  • this total amount is 10% by weight or more, there are tendencies that texture, heat-resistance and the like of the resulting molded article are excellent and shrinkage rate in curing lowers.
  • this total amount is 90% by weight or less, flowability in molding the acrylic premix or acrylic SMC or BMC is improved, and gloss and impact-resistance of the resulting molded article are excellent.
  • the lower limit of this total amount is preferably 20% by weight or more, particularly preferably 40% by weight or more.
  • the upper limit thereof is more preferably 80% by weight or less, particularly preferably 70% by weight or less.
  • the production method of the inorganic filler-containing resin particle (D) is not particularly restricted, and there is exemplified a method in which a resin molded article containing an inorganic filler obtained by polymerization and curing according to a heat press method, casting method and the like is ground, and the resulted ground particles are classified.
  • a resin molded article containing an inorganic filler obtained by polymerization and curing according to a heat press method, casting method and the like is ground, and the resulted ground particles are classified.
  • an acrylic artificial marble molded article so molded is ground and the resulted ground particles are classified.
  • the inorganic filler-containing resin particle (D) one particle may be used or two or more particles having different colors and particle sizes may be used.
  • the particle size of the inorganic filler-containing resin particle (D) is not particularly restricted, providing it is not more than the thickness of a molded article.
  • various additives can be added if required such as reinforcing agents like glass fiber, carbon fiber and the like; coloring agents; internal releasing agents; low shrinkage agents; polymerization inhibitors; and the like, in addition to the above-described components (A) to (D).
  • the mixing method of various constituent components for obtaining the acrylic premix of the present invention is not particularly restricted.
  • the above-described component (a1), component (a2), component (b), component (B), component (C), and if required component (D) and other additive components may be mixed at one time; or the component (a1) may be partially polymerized previously to form a component (b) as a polymerized material thereof in the component (a1), then, the remaining components may be mixed; or a part or all of the component (b) may be previously dissolved in the component (a1) and/or component (a2) to form a syrup, then, the remaining components may be mixed.
  • the apparatus for mixing various constituent components is not particularly restricted, and for example, a kneader, mixer, roll and the like can be used.
  • the kneading time is not particularly restricted, and preferably within 10 minutes.
  • the kneading time is 10 minutes or less, there is tendency that storage stability of the acrylic premix is excellent since the total amount of the heat which the acrylic premix receives in kneading decreases.
  • the inorganic filler-containing resin particle (D) is compounded to produce a granite-like acrylic premix, there are tendencies that swelling and dissolution of the inorganic filler-containing resin particle (D) in the acrylic mono-functional monomer (a1) and/or acrylic poly-functional monomer (a2) are suppressed and the resulting artificial marble is endowed with clear grain pattern providing excellent appearance.
  • the kneading time is preferably 2 minutes or less, particularly preferably 1 minute or less.
  • the lower limit thereof is not particularly restricted, and preferably 10 seconds or more, more preferably 20 seconds or more.
  • the acrylic SMC or BMC of the present invention is thickened to level revealing no stickiness in such a short period of time, handling thereof is excellent even immediately after discharged from a continuous twin screw kneader. Also this acrylic SMC or BMC may be subjected to press molding without aging after discharged from a continuous twin screw kneader, or if necessary, may be aged before press molding after discharged from a continuous twin screw kneader.
  • acrylic artificial marble By curing the acrylic premix of the present invention, acrylic artificial marble can be produced having such excellent impact-resistance as an Izod impact value of 8.0 kJ/m 2 or more.
  • acrylic premix of the present invention there can also be produced acrylic artificial marble having an Izod impact value of 10.0 kJ/m 2 or more.
  • Curing method of the acrylic premix is not particularly restricted, and the acrylic premix may be as it is heat-cured by a casting method or redox-cured, or the acrylic premix may be converted to an acrylic SMC or BMC using a thickening agent before heat and press curing.
  • a method in which an acrylic premix is thickened to obtain an acrylic SMC or BMC which is then subjected to heat and press curing has high productivity and is preferable.
  • the deflection temperature under load of the acrylic artificial marble of the present invention is not particularly restricted, however, when the acrylic premix of the present invention is converted to an acrylic SMC or BMC before heat and press curing, the deflection temperature under load thereof is preferably 70° C. or more.
  • the deflection temperature under load of acrylic artificial marble is 70° C. or more, there is tendency that a molded article obtained by heat and press curing of an acrylic SMC or BMC can be taken out without deformation in taking out the molded article from a mold.
  • the lower limit of this deflection temperature under load is more preferably 80° C. or more, particularly preferably 90° C. or more, most preferably 100° C. or more.
  • the upper limit thereof is not particularly restricted, and preferably 130° C. or less, more preferably 120° C. or less.
  • the production can be conducted by a known method such as a press molding method, transfer molding method, injection molding method, extrusion molding method and the like.
  • the heating temperature is not particularly restricted, and preferably in the range from 80 to 150° C.
  • the heating temperature is 80° C. or more, the curing time can be reduced and productivity tends to be higher, and when 150° C. or less, appearance of the resulting molded article tends to be excellent.
  • the lower limit of this heating temperature is more preferably 90° C. or more, particularly preferably 105° C. or more.
  • the upper limit thereof is more preferably 140° C. or less, particularly preferably 135° C. or less. Further, heat-curing may be conducted maintaining temperature difference between an upper mold and a lower mold in this temperature range.
  • the pressing value is preferably in the range from 1 to 20 MPa.
  • this pressing value is 1 MPa or more, filling property of an acrylic SMC or BMC into a mold tends to be excellent, and when 20 MPa or less, excellent appearance of a mold article tends to be obtained.
  • the lower limit of the pressing value is more preferably 2 MPa or more, and the upper limit thereof is more preferably 15 MPa or less.
  • the molding time may be appropriately selected depending on the thickness of a molded article.
  • Average particle size It was measured using laser scattering particle size distribution analyzer (LA-910, manufactured by HORIBA Ltd.)
  • Oil absorption It was measured according to JIS K 5101-1991, and time directly before a putty-like lamp is steeply softened with the last one drop of linseed oil was recognized as terminal point.
  • Specific surface area It was measured by a nitrogen adsorption method using a surface area meter SA-6201 (manufactured by HORIBA Ltd.).
  • Weight average molecular weight It is a value calculated in terms of polystyrene according to a GPC method, and was measured according to any of the following conditions depending on the range of the weight-average molecular weight.
  • High performance GPC apparatus HLC-8120 manufactured by Tosoh Corp.
  • TSKgelG2000HXL and TSKgelG4000HXL are connected in series, manufactured by Tosoh Corp.
  • Oven temperature 40° C.
  • RI differential refractometer
  • High performance GPC apparatus HLC-8020 manufactured by Tosoh Corp.
  • TSKgelGMHXL Three of TSKgelGMHXL are connected in series, manufactured by Tosoh Corp.
  • Oven temperature 38° C.
  • RI differential refractometer
  • High performance GPC apparatus HLC-8020 manufactured by Tosoh Corp.
  • TSKgelGMHHR-H(30) Two of TSKgelGMHHR-H(30) are connected in series, manufactured by Tosoh Corp.
  • Oven temperature 40° C.
  • RI differential refractometer
  • Degree of swelling A polymer powder was charged in a 100 ml measuring cylinder, the cylinder was tapped weakly several times to compact the powder to 5 ml, then, to this was charged methyl methacrylate cooled to 10° C. or lower so that the total amount was 100 ml, and the mixture was stirred quickly until the mixture became totally uniform, then, the measuring cylinder was kept in a thermostat at 25° C. for 1 hour, the volume of the polymer powder layer after swelling was measured, and the degree of swelling was represented by ratio to the volume (5 ml) of the polymer powder layer before swelling.
  • BMC obtained from an acrylic premix was placed in to a sealed vessel, stored in an atmosphere at 23° C. and the storage stability was evaluated according to the following criteria.
  • Deflection temperature under load It was determined according to JIS K-6911-1995. A 12.7 mm ⁇ 127 mm plate was cut out from an artificial marble plate having a thickness of 3.2 mm to obtain a specimen having a width of 3.2 mm, a height of 12.7 mm and a length of 127 mm. Such weight was used that bending modulus was 1.80 N/mm 2.
  • Izod impact value It was determined according to JIS K-7110-1984. A 12.7 mm ⁇ 64 mm plate was cut out from an artificial marble plate having a thickness of 10 mm to obtain a specimen, and the edgewise impact value was determined without notch.
  • a molded plate was immersed in hot water of 80° C. for 120 hours, and color changes (whiteness, color difference) thereof were compared based on the plate before the immersion.
  • the resulted non-crosslinked polymer powder (P-1) had a weight-average molecular weight of 600,000, and was completely dissolved in methyl methacrylate and had a degree of swelling of 20-fold or more.
  • Other physical properties are shown in Table 1.
  • the resulted non-crosslinked polymer powder (P-2) had a weight-average molecular weight of 40,000 and a degree of swelling by methyl methacrylate was 1.2.
  • Other physical properties are shown in Table 1.
  • this acrylic BMC was filled in a mold for flat plate molding of 200 mm square and was cured with heating and pressing for 10 minutes under conditions of a upper mold temperature of 130° C., a lower mold temperature of 115° C. and a pressure of 10 MPa, to obtain white or black acrylic artificial marble having a thickness of 10 mm.
  • the resulted acrylic artificial marble was ground by a crusher to obtain a white or black inorganic filler-containing resin particle having an average particle size of 350 ⁇ m.
  • the powdery properties thereof are shown in Table 2.
  • this acrylic BMC was filled in a mold for flat plate molding of 200 mm square and was cured with heating and pressing for 10 minutes under conditions of a upper mold temperature of 130° C., a lower mold temperature of 115° C. and a pressure of 10 MPa, to obtain acrylic artificial marble having a thickness of 10 mm.
  • Defect such as deformation and the like was not recognized in taking the resulted artificial marble out of a mold, and the artificial marble could be taken out without problem.
  • the surface of the resulted artificial marble was in mirror-like condition having extremely high gloss and no deficiency at all.
  • This artificial marble had an Izod impact value of 12.0 kJ/m 2 and a falling ball impact height of 85 cm.
  • a flat plate having a thickness of 3.2 mm was separately molded using this acrylic BMC by the same method, and deflection temperature under load was evaluated to find it was 103° C.
  • This acrylic BMC was left at 23° C., then, it was not cured even after 3 months and storage stability was excellent.
  • An acrylic BMC and acrylic artificial marble were obtained in the same manners as in Example I-2 except that the amount of methyl methacrylate was changed to 16 parts, the amount of tetraethylene glycol dimethacrylate was changed to 5 parts, the amount of the polymer powder (P-1) was changed to 14 parts, and the weight of aluminum hydroxide was changed to 65 parts.
  • the evaluation results are shown in Table 4.
  • the evaluation results are shown in Table 4.
  • the evaluation results are shown in Table 4.
  • Table 4 The evaluation results are shown in Table 4.
  • this acrylic BMC was filled in a mold for flat plate molding of 200 mm square and was cured with heating and pressing the under conditions as in Example I-1. After curing, the resulted molded article was deformed and whitening occurred when the molded article was taken out from a mold. Further the resulted acrylic artificial marble showed no unevenness in gloss on the surface thereof, however, gloss was low overall. The deflection temperature under load of this acrylic artificial marble was evaluated to find it was as low as 67° C. Other physical properties are shown in Table 4.
  • This acrylic BMC was left at 23° C., then, it was cured in two weeks and the storage stability was poor.
  • the deflection temperature under load of this acrylic artificial marble was as high as 126° C., and though it was not deformed particularly in being taken out from a mold, the Izod impact value was 6.2 kJ/m 2 , the falling ball impact height was 40 cm, namely the impact-resistance was low.
  • the deflection temperature under load of this acrylic artificial marble was as high as 126° C., and though it was not deformed particularly in being taken out from a mold, the Izod impact value was 6.4 kJ/m 2 , the falling ball impact height was 45 cm, namely the impact-resistance was low.
  • Table 6 The evaluation results are shown in Table 6.
  • the deflection temperature under load of this acrylic artificial marble was as high as 124° C., and though it was not deformed particularly in being taken out from a mold, the Izod impact value was 6.4 kJ/m 2 , the falling ball impact height was 45 cm, namely the impact-resistance was low.
  • Table 8 The evaluation results are shown in Table 8.
  • the deflection temperature under load of this acrylic artificial marble was as high as 122° C., and though it was not deformed particularly in being taken out from a mold, the Izod impact value was 6.7 kJ/m 2 , the falling ball impact height was 50 cm, namely the impact-resistance was low.
  • R 1 represents a hydrogen atom
  • R 2 represents a dimethylethylene group
  • the deflection temperature under load of this acrylic artificial marble was as high as 95° C., and though it was not deformed particularly in being taken out from a mold, the Izod impact value was 8.4 kJ/m 2 , the falling ball impact height was 60 cm, namely the impact-resistance was low.
  • the evaluation results are shown in Table 12.
  • the evaluation results are shown in Table 12.
  • Table 12 The evaluation results are shown in Table 12.
  • this acrylic BMC was filled in a mold for flat plate molding of 200 mm square and was cured with heating and pressing under the conditions as in Example I-1. After curing, the resulted molded article was deformed and whitening occurred when the molded article was taken out from a mold. Further the resulted acrylic artificial marble showed no unevenness in gloss on the surface thereof, however, gloss was low overall. The deflection temperature under load of this acrylic artificial marble was evaluated to find it was as low as 60° C. Other physical properties are shown in Table 12.
  • MMA methyl methacrylate
  • CHMA cyclohexyl methacrylate
  • IBXMA isobornyl methacrylate
  • ST styrene
  • 3G triethylene glycol dimethacrylate
  • 4G tetraethylene glycol dimethacrylate
  • EDMA ethylene glycol dimethacrylate
  • NPG neopentyl glycol dimethacrylate
  • KD-1 t-amyl peroxy benzoate
  • 3M 1,1-bis(di-t-butyl peroxy) 3,3,5-trimethylcyclohexane
  • AN t-amyl peroxy-3,5,5-trimethylhexanoate
  • BPO benzoyl peroxide
  • MMA methyl methacrylate
  • CHMA cyclohexyl methacrylate
  • ST styrene
  • 3G triethylene glycol dimethacrylate
  • NPG neopentyl glycol dimethacrylate
  • KD-1 t-amyl peroxy benzoate
  • 3M 1,1-bis(di-t-butyl peroxy) 3,3,5-trimethylcyclohexane
  • AN t-amyl peroxy-3,5,5-trimethylhexanoate
  • III-5 7 3 3 — — — — 9 12 46 20 3M 0.5 0.15 Ex. III-6 15 — — 9 — — — 10 46 20 KD-1 0.5 0.15 Ex. III-7 19 — — 5 — — — — 10 46 20 KD-1 0.5 0.15
  • Table 7 Abbreviations in Table 7 are shown below.
  • MMA methyl methacrylate
  • CHMA cyclohexyl methacrylate
  • 3G triethylene glycol dimethacrylate
  • BDMA 1,4-butylene glycol dimethacrylate
  • NPG neopentyl glycol dimethacrylate
  • KD-1 t-amyl peroxy benzoate
  • 3M 1,1-bis(di-t-butyl peroxy) 3,3,5-trimethylcyclohexane
  • AN t-amyl peroxy-3,5,5-trimethylhexanoate
  • MMA methyl methacrylate
  • ST styrene
  • HX620 Kayarad HX-620
  • HX220 Kayarad HX-220
  • MANDA Kayarad MANDA
  • NPG neopentyl glycol dimethacrylate
  • KD-1 t-amyl peroxy benzoate
  • AN t-amyl peroxy-3,5,5-trimethylhexanoate
  • MMA methyl methacrylate
  • CHMA cyclohexyl methacrylate
  • ST styrene
  • 3G triethylene glycoldimethacrylate
  • NPG neopentyl glycol dimethacrylate
  • KD-1 t-amyl peroxy benzoate
  • 3M 1,1-bis(di-t-butyl peroxy) 3,3,5-trimethylcyclohexane
  • AN t-amyl peroxy-3,5,5-trimethylhexanoate
  • an acrylic premix which provides an acrylic SMC or BMC which is suitable for molding at high temperature, excellent in molding processability, has excellent thickening property and has excellent storage stability by compounding an acrylic poly-functional monomer having specific structure in the present invention, and further, acrylic artificial marble produced using this has excellent appearance and high impact-resistance, therefore is industrially very useful.
US09/698,046 1998-04-28 2000-10-30 Acrylic premix, acrylic artificial marble and production method thereof Expired - Fee Related US6451910B1 (en)

Applications Claiming Priority (11)

Application Number Priority Date Filing Date Title
JP10-118977 1998-04-28
JP10-118978 1998-04-28
JP11898098 1998-04-28
JP11897798 1998-04-28
JP10-118980 1998-04-28
JP11897898 1998-04-28
JP11897998 1998-04-28
JP10-118979 1998-04-28
JP25367898 1998-09-08
JP10-253678 1998-09-08
PCT/JP1999/002225 WO1999055633A1 (fr) 1998-04-28 1999-04-27 Premix acrylique, faux marbre acrylique et leur production

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1999/002225 Continuation WO1999055633A1 (fr) 1998-04-28 1999-04-27 Premix acrylique, faux marbre acrylique et leur production

Publications (1)

Publication Number Publication Date
US6451910B1 true US6451910B1 (en) 2002-09-17

Family

ID=27526819

Family Applications (1)

Application Number Title Priority Date Filing Date
US09/698,046 Expired - Fee Related US6451910B1 (en) 1998-04-28 2000-10-30 Acrylic premix, acrylic artificial marble and production method thereof

Country Status (6)

Country Link
US (1) US6451910B1 (ja)
EP (1) EP1081111A1 (ja)
JP (1) JP4377055B2 (ja)
KR (1) KR20010043076A (ja)
CN (1) CN1102548C (ja)
WO (1) WO1999055633A1 (ja)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6559254B2 (en) * 2000-02-14 2003-05-06 Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha Method of producing a vinyl acetate polymer and its saponification product
US20030096887A1 (en) * 2001-11-06 2003-05-22 Nobuhiko Yukawa Artificial marble and producing method thereof
US20050053730A1 (en) * 2003-07-29 2005-03-10 Bong-Hyun Kwon Artificial marble reutilizing waste materials and preparation thereof
US20050090597A1 (en) * 2003-10-28 2005-04-28 Chirag Parekh Aggregate for making a molded article and a method of making the aggregate
US20110178228A1 (en) * 2008-10-08 2011-07-21 Kim Hang Young Resin syrup, artificial marble containing a hardened form of the resin syrup, and a production method for the same
CN102352068A (zh) * 2011-08-01 2012-02-15 广东晨宝复合材料有限公司 一种石木塑复合材料
US20130196148A1 (en) * 2010-10-19 2013-08-01 Lg Hausys, Ltd. Synthetic acrylic marble having pearl-containing patterns and method of producing the same
US9469745B2 (en) 2012-10-25 2016-10-18 Kohler Co Engineered composite material and products produced therefrom
RU2751194C1 (ru) * 2019-09-25 2021-07-12 Шок Гмбх Теплоотверждаемая литейная масса на биооснове, изготовленное из нее формованное тело, а также способ изготовления такого формованного тела
US20220025169A1 (en) * 2020-07-22 2022-01-27 Schock Gmbh Heat-curable biobased casting composition, shaped article produced therefrom and process for producing such a shaped article
RU2776994C1 (ru) * 2020-07-22 2022-07-29 Шок Гмбх Термоотверждаемая литейная масса на биооснове, изготовленное из нее формованное тело, а также способ изготовления такого формованного тела
US11685692B2 (en) * 2019-10-07 2023-06-27 Waps Co., Ltd Composition for manufacturing artificial marble

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003073430A (ja) * 2001-09-04 2003-03-12 Sumitomo Chem Co Ltd 樹脂組成物、成形体および成形体の製造方法
ITVR20070078A1 (it) * 2007-06-05 2008-12-06 Aros Srl Composizione e procedimento per l'ottenimento di un materiale lapideo artificiale
KR101172385B1 (ko) * 2008-12-15 2012-08-08 제일모직주식회사 인조대리석용 마블칩, 그 제조방법 및 이를 포함하는 인조대리석
WO2011033998A1 (ja) * 2009-09-15 2011-03-24 三菱レイヨン株式会社 重合性組成物及びアクリル樹脂フィルム
WO2011087008A1 (ja) * 2010-01-14 2011-07-21 三菱レイヨン株式会社 硬化性樹脂組成物、その硬化物からなる光学部材
KR101338626B1 (ko) 2010-08-27 2013-12-06 (주)엘지하우시스 화강암 패턴의 아크릴계 인조대리석 및 그 제조방법
TWI572622B (zh) * 2010-08-31 2017-03-01 三菱麗陽股份有限公司 丙烯酸系組成物、成形體、行動電話鍵片材及導光體
JP5700245B2 (ja) * 2011-03-09 2015-04-15 三菱レイヨン株式会社 アクリル樹脂板、アクリル樹脂積層体及び表示装置
GB201604077D0 (en) * 2016-03-09 2016-04-20 Lucite Int Uk Ltd A composition for synthetic stone
KR102171641B1 (ko) * 2017-04-18 2020-10-29 (주)엘지하우시스 인조 대리석용 조성물 및 인조 대리석
CN106986578A (zh) * 2017-05-03 2017-07-28 珠海市盛西源机电设备有限公司 一种人造大理石的亚克力实体面材及其制备方法
KR20220110767A (ko) * 2019-11-29 2022-08-09 쇼와덴코머티리얼즈가부시끼가이샤 폴리옥시알킬렌쇄를 갖는 화합물을 함유하는 조성물 세트

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03257048A (ja) 1990-03-07 1991-11-15 Nippon Shokubai Co Ltd 耐衝撃性および切削加工性に優れた人工大理石
US5149776A (en) 1989-11-17 1992-09-22 Mitsubishi Rayon Co., Ltd. Cross-linking hardenable resin composition, metal laminates thereof and metal surface processing method therewith
JPH0578545A (ja) 1991-09-18 1993-03-30 Mitsubishi Rayon Co Ltd アクリル系シラツプ組成物
US5356754A (en) 1992-09-25 1994-10-18 Mitsubishi Rayon Co., Ltd. Crosslinking curable resin composition
JPH09111084A (ja) 1995-10-13 1997-04-28 Mitsubishi Rayon Co Ltd 樹脂組成物、アクリル系プリミックス及びアクリル系人工大理石の製造方法
US6028127A (en) * 1994-10-14 2000-02-22 Mitsubishi Rayon Co., Ltd. Artificial marble and method for preparing it
JP3257048B2 (ja) 1992-06-30 2002-02-18 株式会社島津製作所 医療用寝台

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62212441A (ja) * 1986-03-14 1987-09-18 Nippon Shokubai Kagaku Kogyo Co Ltd 耐熱・耐熱水性にすぐれた硬化物を与えるプレミツクス成形材料
JPH06298883A (ja) * 1993-04-14 1994-10-25 Dainippon Ink & Chem Inc 成形材料及び人工大理石の製造方法
KR100356886B1 (ko) * 1994-12-30 2003-01-08 이 아이 듀폰 디 네모아 앤드 캄파니 인조대리석판
KR100348548B1 (ko) * 1995-08-16 2002-10-31 이 아이 듀폰 디 네모아 앤드 캄파니 내약품성이향상된인조대리석판의제조방법

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5149776A (en) 1989-11-17 1992-09-22 Mitsubishi Rayon Co., Ltd. Cross-linking hardenable resin composition, metal laminates thereof and metal surface processing method therewith
JPH03257048A (ja) 1990-03-07 1991-11-15 Nippon Shokubai Co Ltd 耐衝撃性および切削加工性に優れた人工大理石
JPH0578545A (ja) 1991-09-18 1993-03-30 Mitsubishi Rayon Co Ltd アクリル系シラツプ組成物
JP3257048B2 (ja) 1992-06-30 2002-02-18 株式会社島津製作所 医療用寝台
US5356754A (en) 1992-09-25 1994-10-18 Mitsubishi Rayon Co., Ltd. Crosslinking curable resin composition
US6028127A (en) * 1994-10-14 2000-02-22 Mitsubishi Rayon Co., Ltd. Artificial marble and method for preparing it
JPH09111084A (ja) 1995-10-13 1997-04-28 Mitsubishi Rayon Co Ltd 樹脂組成物、アクリル系プリミックス及びアクリル系人工大理石の製造方法

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6559254B2 (en) * 2000-02-14 2003-05-06 Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha Method of producing a vinyl acetate polymer and its saponification product
US20030096887A1 (en) * 2001-11-06 2003-05-22 Nobuhiko Yukawa Artificial marble and producing method thereof
US6946508B2 (en) * 2001-11-06 2005-09-20 Nippon Shokubai Co. Ltd. Artificial marble and producing method thereof
US20050053730A1 (en) * 2003-07-29 2005-03-10 Bong-Hyun Kwon Artificial marble reutilizing waste materials and preparation thereof
EP1514854A1 (en) 2003-07-29 2005-03-16 LG Chem. Ltd. Artificial marble comprising waste acrylic materials and preparation thereof
US7427642B2 (en) 2003-07-29 2008-09-23 Lg Chem. Ltd. Artificial marble reutilizing waste materials and preparation thereof
US20050090597A1 (en) * 2003-10-28 2005-04-28 Chirag Parekh Aggregate for making a molded article and a method of making the aggregate
US7625445B2 (en) * 2003-10-28 2009-12-01 Chirag Parekh Aggregate for making a molded article and a method of making the aggregate
US20110178228A1 (en) * 2008-10-08 2011-07-21 Kim Hang Young Resin syrup, artificial marble containing a hardened form of the resin syrup, and a production method for the same
US8927625B2 (en) * 2008-10-08 2015-01-06 Lg Hausys, Ltd. Resin syrup, artificial marble containing a hardened form of the resin syrup, and a production method for the same
US20130196148A1 (en) * 2010-10-19 2013-08-01 Lg Hausys, Ltd. Synthetic acrylic marble having pearl-containing patterns and method of producing the same
CN102352068B (zh) * 2011-08-01 2013-02-20 广东晨宝复合材料有限公司 一种石木塑复合材料
CN102352068A (zh) * 2011-08-01 2012-02-15 广东晨宝复合材料有限公司 一种石木塑复合材料
US9469745B2 (en) 2012-10-25 2016-10-18 Kohler Co Engineered composite material and products produced therefrom
US9650490B2 (en) 2012-10-25 2017-05-16 Kohler Co. Method of making an engineered composite material and products produced therefrom
RU2751194C1 (ru) * 2019-09-25 2021-07-12 Шок Гмбх Теплоотверждаемая литейная масса на биооснове, изготовленное из нее формованное тело, а также способ изготовления такого формованного тела
IL276837B1 (en) * 2019-09-25 2023-08-01 Schock Gmbh Casting composition based on biological material that can be cured with heat, a mold made from it and a method for making such a mold
US11685692B2 (en) * 2019-10-07 2023-06-27 Waps Co., Ltd Composition for manufacturing artificial marble
US20220025169A1 (en) * 2020-07-22 2022-01-27 Schock Gmbh Heat-curable biobased casting composition, shaped article produced therefrom and process for producing such a shaped article
RU2776994C1 (ru) * 2020-07-22 2022-07-29 Шок Гмбх Термоотверждаемая литейная масса на биооснове, изготовленное из нее формованное тело, а также способ изготовления такого формованного тела

Also Published As

Publication number Publication date
EP1081111A1 (en) 2001-03-07
CN1102548C (zh) 2003-03-05
WO1999055633A1 (fr) 1999-11-04
CN1302281A (zh) 2001-07-04
JP4377055B2 (ja) 2009-12-02
KR20010043076A (ko) 2001-05-25

Similar Documents

Publication Publication Date Title
US6451910B1 (en) Acrylic premix, acrylic artificial marble and production method thereof
EP0976786A1 (en) (meth)acrylic premix, (meth)acrylic smc or bmc, and process for producing (meth)acrylic artificial marble
JP4222724B2 (ja) アクリル系ｓｍｃ又はｂｍｃ
US20030045628A1 (en) (meth) acrylic resin composition for thermosetting type injection molding, method for producing the same and method for producing (meth) acrylic resin molded article
US6316548B1 (en) (Meth)acrylic premix, (meth)acrylic SMC or BMC, and process producing (meth)acrylic artificial marble
EP1146023A1 (en) Acrylic smc or bmc, process for producing the same, process for producing artificial acrylic marble, and thickener
JP3486537B2 (ja) アクリル系樹脂組成物、プレミックス、ｓｍｃ又はｂｍｃ、及び人工大理石の製造方法
JP3527638B2 (ja) （メタ）アクリル系プレミックス、（メタ）アクリル系ｓｍｃ又はｂｍｃ、及び（メタ）アクリル系人工大理石の製造方法
JP3561410B2 (ja) （メタ）アクリル系プレミックス、（メタ）アクリル系ｓｍｃ又はｂｍｃ、及び（メタ）アクリル系人工大理石の製造方法
EP0474203B1 (en) Reactive particulate resin, method for producing the same, and resin composition for thermoforming
JP3545944B2 (ja) （メタ）アクリル系プレミックス、（メタ）アクリル系ｓｍｃ又はｂｍｃ、及び（メタ）アクリル系人工大理石の製造方法
JPH09111084A (ja) 樹脂組成物、アクリル系プリミックス及びアクリル系人工大理石の製造方法
JPH04363313A (ja) 反応性樹脂微粒子、その製造法および加熱成形用樹脂組成物
JP2001038724A (ja) アクリル系シート・モールディング・コンパウンド（ｓｍｃ）、そのｓｍｃを用いたアクリル系樹脂成形品、およびその製造方法
JP3443012B2 (ja) （メタ）アクリル系プレミックス、（メタ）アクリル系ｓｍｃ又はｂｍｃ、及び（メタ）アクリル系人工大理石の製造方法
JP3370549B2 (ja) アクリル系樹脂組成物、アクリル系プレミックス、アクリル系人工大理石の製造方法及び増粘剤
JPH09111085A (ja) 樹脂組成物、アクリル系プリミックス及びアクリル系人工大理石の製造方法
JP3433890B2 (ja) アクリル系樹脂組成物、アクリル系プレミックス、アクリル系ｓｍｃ又はｂｍｃ、及びアクリル系人工大理石の製造方法
JP3370546B2 (ja) アクリル系プレミックス及び石目調アクリル系人工大理石
JP2000063613A (ja) アクリル系プレミックス、アクリル系ｓｍｃ又はｂｍｃ、及びアクリル系人工大理石の製造方法
JP2000026557A (ja) アクリル系プレミックス、アクリル系人工大理石の製造方法
JP3361034B2 (ja) アクリル系樹脂組成物、アクリル系プレミックス、アクリル系ｓｍｃ又はｂｍｃ、及びアクリル系人工大理石の製造方法
JPH09110497A (ja) 樹脂組成物、アクリル系プリミックス及びアクリル系人工大理石の製造方法
EP1197523A1 (en) Method for producing acrylic bmc, method for producing acrylic syrup, and method for producing acrylic molded article
JP2001040164A (ja) シート・モールディング・コンパウンド用アクリル系樹脂組成物

Legal Events

Date Code Title Description
AS Assignment

Owner name: MITSUBISHI RAYON CO., LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KOYANAGI, SEIYA;SAIKI, SHINJI;KISHIMOTO, YUICHIRO;REEL/FRAME:011431/0078

Effective date: 20001121

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Free format text: PAYER NUMBER DE-ASSIGNED (ORIGINAL EVENT CODE: RMPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20060917